Sizing composition for glass yarns, method using composition and resulting products

ABSTRACT

The present invention relates to a sizing composition for glass strands, consisting of a solution whose solvent content is less than or equal to 5% by weight, this solution comprising at least 45% by weight of components capable of curing, these components being, in respect of at least 40% of them, components with a molecular mass of between 750 and 5000 and these curable components comprising at least one mixture capable of curing:  
     one or more components having at least one acrylic and/or methacrylic functional group and  
     one or more components having at least one primary and/or secondary amine functional group.  
     The invention also relates to a process using this composition, to the strands coated with said composition and to the composites obtained from these strands.

[0001] The present invention relates to the field of reinforcing fibers,especially for the production of composites. It relates to a sizingcomposition for glass strands, to a process for preparing said strandsusing this composition and to the glass strands obtained and thecomposites produced from these strands.

[0002] It is known to manufacture glass reinforcing strands from streamsof molten glass flowing out of the orifices of bushings. These streamsare drawn in the form of continuous filaments, then these filaments areassembled into base strands, which are then collected.

[0003] Before they are assembled in the form of strands, the filamentsare usually coated with a size or sizing composition by passing themthrough a sizer. This deposition of size is very important as it makesit possible, on the one hand, to obtain the strands and, on the otherhand, to use these strands effectively in making up composites. The sizehas the following usual functions: it protects the strands fromabrasion, thus preventing them from breaking during their manufactureand possibly during their use; it allows the strands thus formed to becombined with organic and/or inorganic materials to be reinforced,especially making it easier for the strands to be wetted by andimpregnated with these materials.

[0004] In general, the size thus favors adhesion between the glass andthe material to be reinforced, thereby making it possible to obtaincomposites having improved mechanical properties.

[0005] The size may also ensure integrity of the strands, that is to saymay allow the filaments to be linked together within the strands. Thisintegrity is desired especially in applications in which the strands aresubjected to high mechanical stresses, such as textile applications.This is because filaments that are not strongly attached to each otherhave a tendency to break, which disrupts the proper functioning of thetextile machines.

[0006] Furthermore, strands with no integrity are known to be difficultto handle.

[0007] In general, the sizing compositions must also be able towithstand the shear induced by passage of the strands over the drawingdevices and to wet the surface of the filaments, and to do so at highdrawing speeds of the order of several tens of meters per second.

[0008] Moreover, it is recommended to choose sizing compositions fromthose which preserve their initial properties over time.

[0009] These compositions must not be able to react at the storagetemperature (in general below 30° C.) or even at a higher temperaturesuch as that which may be encountered beneath the bushing (of around80-100° C.), as then the increase in the viscosity is such that it isdifficult, or even impossible, to deposit the size on the filaments.

[0010] The sizes most commonly employed are low-viscosity aqueous sizeswhich are easy to use but must be deposited in large amounts on thefilaments. Water generally represents more than 80% by weight of thesize, which requires the strands to be dried before they are used, sincethe water may cause, among other things, a reduction in the adhesionbetween the strands and the material to be reinforced. Drying by heattreatment is a lengthy and expensive operation which needs to beperfectly matched to the strand manufacturing conditions. Such atreatment is not neutral with regard to the sized strand. When the sizedstrand is especially wound in the form of packages, the following mayoccur: modification in the distribution of the constituents of the sizeby irregular and/or selective migration, coloration of the strand anddeformation of the package. The deformation is also observed, in theabsence of drying, on straight-sided packages (or rovings) of finestrands (linear density or strand count of less than 600 tex (g/km))coated with an aqueous size.

[0011] To solve the aforementioned problems, so-called anhydrous sizingcompositions have been proposed, that is to say those which compriseless than 5% by weight of solvent. Such compositions are described, forexample, in the following patent applications:

[0012] FR-A-2 727 972 proposes a composition for the size of glassstrands which cures by UV radiation or an electron beam. Thiscomposition has a viscosity of less than or equal to 400 cP andcomprises a curable base system which contains at least one componentwith a molecular mass of less than 750 having at least one epoxyfunctional group and comprising at least 60% by weight of one or morecomponents with a molecular mass of less than 750 having at least oneepoxy, hydroxyl, vinyl ether, acrylic or methacrylic functional group.

[0013] FR-A-2 772 369 describes a sizing composition for glass strands,which does not require a drying step after deposition on the strand.This composition comprises at least 60% by weight of components capableof curing, these components being, in respect of least 60% of them,components with a molecular mass of less than 750 and these curablecomponents comprising at least one mixture of component(s) having atleast one acrylic and/or methacrylic reactive functional group andcomponent(s) having at least one primary amine and/or secondary aminefunctional group, at least 20% by weight of these components having atleast two acrylic, methacrylic, primary amine and/or secondary aminereactive functional groups.

[0014] The anhydrous compositions that have just been mentioned containa high proportion of monomers capable of polymerizing at roomtemperature. Given that very little time, in general less than 1 second,elapses between deposition of the composition on the glass filaments andwinding of the strand, the turns of the package are generally coatedwith an incompletely cured size. Under the conditions in which thestrand is wound directly to form a straight-sided package (rovings), thecuring rate is insufficient to allow effective blocking of the firstlayers of strand. As the following layers are built up, the lower layershave a tendency to collapse, thus modifying the dimensionalcharacteristics of the package during winding. The observed defects(deformation, increase in length, etc.) make such packages unusable onthe appropriate devices.

[0015] Under the conditions that have just been mentioned, the sizingcomposition must be able to be deposited on the filaments in the liquidstate and rapidly change to a gelled state while the strand is beingwound. The time needed to reach the gelled state (“gel time”) depends onthe temperature at the time of deposition, which temperature may beabove 100° C. In general, a sizing composition is satisfactory when itsgel time measured at room temperature (around 25° C.) is between 10 and40 minutes, preferably between 15 and 30 minutes.

[0016] Moreover, at the deposition temperature, which may be above 100°C. as mentioned above, the monomers present in the sizing compositionhave a tendency to evaporate because of their relatively high vaporpressure. This results in a reduction in the content of monomers in thecomposition and therefore in a variation in the amount and thecomposition of the size along the strand. Furthermore, the volatilecompounds and certain monomers, especially the amine monomers, areliable to present a risk to the health of those handling them.

[0017] The subject of the present invention is a novel sizingcomposition capable of coating glass strands reliably, rapidly anduniformly over their entire length and resulting in correct packages onsuitable supports, this composition making the strands easy to handleand giving them pliancy compatible with the subsequent treatments, whilepreserving their integrity.

[0018] Another subject of the invention is the glass strands sized bymeans of the composition defined in the above paragraph, said strandshaving mechanical properties that are constant over their entire lengthand being able to reinforce an organic and/or inorganic material inorder to prepare compositions, in particular hollow bodies by winding,fabrics for vehicles and wall reinforcement meshes.

[0019] The sizing composition according to the invention consists of asolution whose solvent content is less than 5% by weight, this solutioncomprising at least 45% by weight of components capable of curing, thesecurable components being, in respect of at least 40% of them, componentswith a molecular mass of between 750 and 5000 and these curablecomponents comprising at least one mixture capable of curing

[0020] one or more components having at least one acrylic and/ormethacrylic reactive functional group and

[0021] one or more components having at least one primary and/orsecondary amine reactive functional group.

[0022] In general, and preferably, at least 40% of the curablecomponents having at least two reactive functional groups chosen fromacrylic, methacrylic, primary amine and secondary amine functionalgroups.

[0023] In the present invention, the following expressions have thefollowing meanings:

[0024] “solvent” is understood to mean water and organic solventscapable of being used to dissolve certain curable components. Thepresence of one or more solvents in a limited amount does not requireparticular treatment in order to remove them. In most cases, the sizesaccording to the invention are completely stripped of solvent;

[0025] “cure”, “curable”, “curing”, etc. are understood to mean “cureand/or crosslink”, “curable and/or crosslinkable”, “curing and/orcrosslinking”, etc., respectively;

[0026] “reactive functional group” is understood to mean a functionalgroup capable of acting in the reaction of curing the size, the curingpossibly taking place at room temperature or at a higher temperature(thermal curing); and

[0027] “curable components” are understood to mean the indispensablecomponents which allow the expected cured structure of the size to beobtained.

[0028] In the rest of the text, “(meth)acrylic component” and “primaryand/or secondary amine component” denote, respectively, a “componenthaving at least one acrylic reactive functional group and/or at leastone methacrylic reactive functional group” and a “component having atleast one primary amine reactive functional group and/or at least onesecondary amine reactive functional group”.

[0029] In the sizing composition according to the invention, the curablecomponents represent between 40 and 100% by weight of the composition,mainly between 45 and 80%, and in most cases between 50 and 70%, byweight. The combination of these curable components is referred tohereafter as the “base system”.

[0030] Preferably, the base system consists predominantly (that is tosay with more than 50%, preferably at least 75% and up to 100% byweight) in most cases of one or more (meth)acrylic components and of oneor more primary and/or secondary amine components, the use of thismixture of components making it possible to obtain, after curing,copolymers contributing appreciably to the structure of the cured size.

[0031] Furthermore, the base system comprises at least 40% (preferablyat least 45% and up to 85% by weight) of component(s) with a molecularmass of between 750 and 5000. In particular, at least 40%, preferably atleast 50% and up to 95% by weight of (meth)acrylic component(s) andprimary and/or secondary amine component(s) have a mass of between 750and 5000.

[0032] It should be pointed out that, in the definition of theinvention, the various contents are evaluated independently of oneanother, the same component possibly occurring with several contents.

[0033] Preferably and in general according to the invention, theaforementioned components with a molecular mass of between 750 and 5000have a molecular mass of less than 3000. Likewise, in most casesaccording to the invention, and preferably, these components aremonofunctional or polyfunctional polymers, as explained below.

[0034] In certain embodiments, the base system according to theinvention may optionally comprise up to 60% of component(s) having amolecular mass of less than or equal to 750, and preferably 15 to 50% byweight of said composition.

[0035] The curable components of the composition according to theinvention may have one or more reactive functional groups. The term“polyfunctional” is defined below as any component having at least tworeactive functional groups. Thus, the expression “(meth)acrylic and/orprimary and/or secondary amine polyfunctional component” is understoodto mean a “component having at least two reactive functional groupschosen from acrylic, methacrylic, primary amine and/or secondary aminefunctional groups”.

[0036] According to the invention, the base system comprises at least40% of (meth)acrylic and/or primary and/or secondary aminepolyfunctional components. Preferably, it comprises between 40 and 100%by weight of this (these) component(s), and better still 50 to 80%,these components being preferably chosen from: components having atleast two acrylic reactive functional groups, components having at leasttwo methacrylic reactive functional groups, components having at leasttwo primary or secondary amine reactive functional groups, componentshaving at least one acrylic reactive functional group and at least onemethacrylic reactive functional group, and components having at leastone primary amine reactive functional group and at least one secondaryamine reactive functional group.

[0037] According to the preferred embodiment of the invention, the basesystem comprises at least one (meth)acrylic polyfunctional componentwith a molecular mass of between 750 and 5000 and at least one primaryamine and/or secondary amine polyfunctional component.

[0038] Preferably, the base system comprises at least one (meth)acrylicpolyfunctional component. In the advantageous embodiments of theinvention, the content of (meth)acrylic polyfunctional component(s) isat least 20% of the base system, and preferably between 30 and 70%.

[0039] Particularly preferably, the base system comprises at least one(meth)acrylic polyfunctional component with a molecular mass of between750 and 5000. In the particularly preferred embodiments of theinvention, at least 20%, preferably 30 to 70%, by weight of thecomponents of the base system are (meth)acrylic polyfunctionalcomponents having a molecular mass of between 750 and 5000.

[0040] As nonlimiting examples, the (meth)acrylic component of thecomposition may be chosen from aliphatic or cycloaliphatic long-chainalkyl (meth)acrylates, aromatic (meth)acrylates, products resulting fromthe esterification of (meth)acrylic acid and a long-chain amino alcohol,products resulting from the reaction of (meth)acrylic acid and apolyalkylene glycol, products resulting from the reaction of(meth)acrylic acid and a polyether-type alcohol, especially a polyetherpolyol, products resulting from the reaction of (meth)acrylic acid and apolyester-type alcohol, especially a polyester polyol, productsresulting from the reaction of (meth)acrylic acid and a product from thereaction of at least one aromatic isocyanate and at least one polyol,and mixtures of these (meth)acrylates.

[0041] As a general rule according to the invention, the proportion ofthe one or more (meth)acrylate components in the sizing composition isbetween 15 and 60% by weight. Preferably, the (meth)acrylicpolyfunctional component(s) represent at least 50% of this (these)(meth)acrylic component(s). As (meth)acrylic polyfunctionalcomponent(s), at least one component having at least three reactivefunctional groups chosen from acrylic and methacrylic functional groupsis preferably used.

[0042] Particularly advantageously, at least one component having fourreactive functional groups chosen from acrylic and methacrylicfunctional groups (tetrafunctional components) and/or a component havingat least six reactive functional groups chosen from acrylic andmethacrylic functional groups (hexafunctional components) is chosen.

[0043] As nonlimiting examples, the primary and/or secondary aminecomponent may be isophoronediamine, methanediamine, N-aminoethylpiperazine, para-phenylenedianiline or meta-phenylenedianiline,oxydianiline, diethyltoluenediamine, 4,4′,-diamino-diphenylmethane, asecondary amine containing an aliphatic chain, diisopentylamine,N-ethylmethylamine, 1-(2-hydroxyethyl)-2-imidazolidinone,2,6-dimethyl-morpholine, 2-propylimidazole, 2,6-diaminopyridine,polyamidoamines, derivatives of polyethylene polyamines, polyoxyalkylenepolyamines, especially polyoxyethylenepolyamines,polyoxypropylenepolyamines, poly(oxyethylene/oxypropylene) polyamines,poly-(oxypropylene/oxybutylene) polyamines, such as4,9-dioxa-1,2-dodecanediamine,N′-(3-amino-propyl)-N,N′-dimethyl-1,3-propane diamine,2-butyl-2-ethyl-1,5-pentanediamine, hexamethylenediamine,meta-xylylenediamine, amino alcohols, amidoamines and mixtures ofprimary amine(s) and phenolic alcohol(s) (Mannich bases).

[0044] As a general rule according to the invention, the proportion ofprimary and/or secondary amine component(s) in the sizing composition isbetween 4 and 40%, preferably between 6 and 25%, by weight.

[0045] In most cases, it is between 6 and 20% of the sizing composition.Preferably, the base system comprises at least one primary and/orsecondary amine polyfunctional component and better still at least onedifunctional component, that is to say one having two reactivefunctional groups chosen from primary and/or secondary amine functionalgroups. Preferably too, the amine functional groups of the primaryand/or secondary amine components are directly attached to an alkylene,cycloalkylene or arylalkylene radical.

[0046] In many cases, the (meth)acrylic component(s) and the primaryand/or secondary amine component(s) are chosen in such a way that theratio r of the number of (meth)acrylic reactive sites to the number ofprimary and/or secondary amine reactive sites present is between 0.15and 3, in order to allow the sizing composition to cure sufficiently. Inmost cases, this ratio r is between 0.3 and 2.5 and preferably between0.4 and 2.

[0047] The sizing composition according to the invention may include, inaddition to the components of the base system, at least one specificcatalyst which increases the rate of the curing reaction, moreparticularly when the curable components are not very reactive.

[0048] It is possible to use a catalyst chosen from tertiary amines,derivatives of tertiary amines and metal halides such as AlCl_(3,)FeCl₃, InCl₃, BF₃ and CuCl₂ or organometallic complexes such asCu-ethylenediamine, Yb acetate and Yb triflate. The catalyst content inthe sizing composition may be up to 8% by weight. In most cases, nocatalyst is used.

[0049] In addition to the aforementioned components which essentiallycontribute to the structure of the cured size, and where appropriate thecatalysts, the sizing composition may include one or more components(hereafter referred to as additives). These additives give the sizeparticular properties and, when the composition is deposited in twosteps, they may be provided by one or both of the compositionsconstituting the size.

[0050] The composition according to the invention may include, asadditive, at least one coupling agent allowing the size to bond to theglass. The coupling agent may be a component of the base system, inwhich case it contributes to the curing reaction, or a component actingonly as additive and not acting in the curing.

[0051] The proportion of coupling agent(s) is generally between 0 and30% by weight, and in most cases greater than 5% by weight, of thesizing composition. Preferably it is between 10 and 25% of thecomposition.

[0052] The coupling agent is generally chosen from silanes such asgamma-glycidoxypropyltrimethoxysilane,gamma-acryloxypropyltrimethoxysilane,gamma-methacryloxypropyltrimethoxysilane,poly(oxyethylene/oxypropylene)-trimethoxysilane,gamma-aminopropyltriethoxysilane, vinyltrimethoxysilane,phenylaminopropyltrimethoxysilane,styrylaminoethylaminopropyltrimethoxysilane ortert-butylcarbamoylpropyltrimethoxysilane, siloxanes, titanates,zirconates and mixtures of these compounds. Preferably, silanes arechosen.

[0053] The composition may include, as additive, at least one textileprocessing aid acting essentially as lubricant, and in many cases thisis necessary so that the composition has the functions of a size.

[0054] The proportion of textile processing aid is generally between 0and 30% by weight of the composition, and preferably 10 to 25%.

[0055] The textile processing aid is generally chosen from among fattyesters such as decyl laurate, isopropyl palmitate, cetyl palmitate,isopropyl stearate, isobutyl stearate, ethylene glycol adipate ortrimethylolpropane trioctanoate, alkyl phenol derivatives such asethoxylated nonyl phenol, derivatives of glycols such as polyethyleneglycols or polypropylene glycols of molecular mass less than 2000,mixtures based on mineral oils, and mixtures of these compounds.

[0056] The composition according to the invention may also include, asadditive, at least one film-forming agent which acts only as a slipagent facilitating the fiberizing process, especially by preventingsubstantial friction between the filaments and the sizer when they arestretched at a high rate and/or when they are very fine. However, thisagent is expensive and may furthermore cause a reduction in themechanical properties of the strands.

[0057] The proportion of film-forming agent is generally less than orequal to 8%, preferably less than or equal to 5%, by weight of thecomposition.

[0058] The film-forming agent is generally chosen from among siliconesand silicone derivatives such as silicone oils, siloxanes andpolysiloxanes such as glycidyl(n)polydimethylsiloxane or alpha,omega-acryloxypolydimethyl siloxane, polyacrylate silicones and mixturesof these compounds.

[0059] The composition according to the invention may include, asadditive, at least one agent adapted to the materials to be reinforced,for example a corrosion inhibitor such as gallic acid in the case ofcementitious materials.

[0060] The composition according to the invention may be deposited onthe glass filaments in one or more steps, for example under theconditions of the process described in FR-A-2 763 328. In this process,streams of molten glass, flowing out from orifices located at the baseof one or more bushings, are drawn in the form of one or more sheets ofcontinuous filaments, then the filaments are assembled into one or morestrands which are collected on one or more moving supports. The size isdeposited to by applying the filaments a first stable composition havinga viscosity of between 20 and 500 cP and at least one second stablecomposition having a viscosity of between 20 and 500 cP, this being fedseparately from the first composition.

[0061] The second composition may be deposited on the filaments at theearliest while the first composition is being deposited or on thestrands at the latest while they are being collected on the supports.The difference in viscosity between the compositions is generally lessthan 250 cP.

[0062] The composition according to the invention is preferably appliedin two steps, the first composition comprising the (meth)acryliccomponent(s) and optionally one or more additives, and the secondcomposition comprising the primary and/or secondary amine component(s)and optionally one or more additives, in particular the curing catalystor catalysts.

[0063] It is particularly advantageous to deposit the size in two steps.This allows better control of the curing reactions and consequently thesize is of uniform quality over the entire length of the strands,ensuring high productivity with a reduced risk of strand breakage. Inmost cases, deposition does not require an external supply of heat.

[0064] The sized strands are generally collected in the form of packageswound onto rotating supports. Whatever the state of cure of the size andthe crossing angle, even when the latter is low (less than 1.5°), it iseasy to unwind the strands from the packages and handle them. Thestraight-sided packages retain their dimensional characteristics and areundeformed.

[0065] The strands may also be collected on receiving supports movingtranslationally. They may in particular be thrown, by a device whichalso serves to draw them, toward the collecting surface which movestransversely to the direction in which the strands are thrown, for thepurpose of obtaining a sheet of entangled continuous strands or “mat”.The strands may also be chopped before they are collected, by a devicealso serving to draw them.

[0066] The strands obtained according to the invention may thus be invarious forms after collection, for example in the form of bobbins ofcontinuous strands (cakes, rovings, cops, etc.), of chopped strands,braids, tapes and mats or meshes. The glass filaments constituting thesestrands have a diameter which may vary greatly, usually from 5 to 30 μm.They may consist of any glass whatsoever, the most common in the fieldof reinforcing yarns being E glass and AR glass.

[0067] The strands obtained according to the invention mayadvantageously be used to reinforce various materials for the purpose ofobtaining composite parts having high mechanical properties. Thecomposites are obtained by combining at least glass strands according tothe invention with at least one organic and/or inorganic material, theglass content generally varying from 2 to 5% by weight (cementitiousmatrix) and from 30 to 75%, preferably 40 to 70%, by weight (organicmatrix). The preferred composites comprise glass strands, predominantly(more than 50% by weight) consisting of the strands according to theinvention, and an organic material, such as a polyester, epoxy orphenolic resin or one of the styrene-butadiene (SBR) type.Advantageously, the resin is a polyester or epoxy resin.

[0068] The examples which follow allow the invention to be illustratedwithout however limiting it.

[0069] In these examples, the following analytical methods were used tomeasure the physical and mechanical properties of the glass strandscoated with the sizing composition according to the invention and of thecomposites containing said strands.

[0070] Glass Strands

[0071] the abrasion resistance was measured by weighing the amount offuzz formed after the strand passes over a series of eight ceramiccylindrical 90° turn rolls. It is expressed in mg per 1 kg of strandtested;

[0072] the stiffness or rigidity was measured under the conditionsdefined by the ISO 3375 standard on 10 test pieces before and afterundergoing the abovementioned abrasion resistance test. The stiffness isexpressed in mm and denoted as x(y), x and y representing the valuemeasured before and the value measured after the strand passes over theturn rolls, respectively. The value y allows pre-assessment of theability of the strand to be impregnated by a material, more particularlyan organic material of the polymer type. In general, a sized glassstrand whose y value is less than 100 mm and preferably close to 60 mm(the lowest value that can be obtained) is satisfactory for applicationsrequiring good impregnation by the matrix. A strand having an x value ofgreater than or equal to 120 and a y value of greater than or equal to100 is suitable for a usage requiring high integrity of the strand;

[0073] the loss on ignition was measured according to the ISO 1887standard. It is expressed in %;

[0074] the tenacity was determined by measuring the tensile strengthunder the conditions in the ISO 3341 standard. It is expressed incN/tex.

[0075] Composites

[0076] the flexural strength and the flexural modulus were measuredunder the conditions defined by the ISO 178 standard, before and afteraging by immersion in water at 100° C. for 24 hours. They are expressedin MPa, the standard deviation σ being calculated over 8 to 10 testpieces;

[0077] the shear strength was measured under the conditions defined bythe ISO 4585 standard, before and after aging by immersion in water at100° C. for 24 hours (examples 1, 4, 6, 9, 12, 14) or 72 hours (examples2-3, 5, 7-8, 10-11, 13, 15). It is expressed in MPa, the standarddeviation σ being calculated over 8 to 10 test pieces.

EXAMPLE 1

[0078] Filaments 13.6 μm in diameter obtained by drawing streams ofmolten E glass, flowing from a bushing (800 orifices), were coated withthe following first composition A and then with the following secondcomposition B (in percentages by weight): Composition A polyestertetraacrylate of molecular mass = 1000⁽¹⁾ 18 aromatic polyurethanehexaacrylate of 18 molecular mass = 1000⁽²⁾gamma-methacryloxypropyltrimethoxysilane⁽³⁾ 11gamma-glycidoxypropyltrimethoxysilane⁽⁴⁾ 10 4-octylphenyl ethyl ether⁽⁵⁾5 Composition B mixture of C,C,C-trimethylhexane-1,6-diamine, 10 ofxylylenediamine and of para-tert-butylphenol⁽⁶⁾ trimethylolpropanetrioctanoate⁽⁷⁾ 15 ethoxylated (4EO) lauric alcohol⁽⁸⁾ 13

[0079] The compositions A and B had a viscosity, measured on a SOFRASERMIVI 4000 apparatus sold by SOFRASER, of 135.4×10⁻³ Pa.s (135.4 cP) and52×10⁻³ Pa.s (52 cP) at 25° C., respectively. The ratio r was 1.66.

[0080] The filaments were assembled as strands which were wound asrovings.

[0081] The amount of fuzz, the stiffness, the loss on ignition, thelinear density and the tenacity were measured on the strands extractedfrom the rovings. The results of these measurements are given in table1.

[0082] From the strands obtained, composite panels having parallelstrands were produced in accordance with the ISO 9291 standard. Theresin used was a resin consisting of 100 parts by weight of isophthalicpolyester (reference: SYNOLIT 1717 sold by DSM) and 1.5 parts by weightof peroxide (reference: HTM 60 sold by Ciba-Geigy).

[0083] The values of the mechanical properties of these composites, inbending and in shear, before and after aging are given in table 2, for aglass content reduced to 100%.

EXAMPLE 2

[0084] From the strands obtained in example 1, composite panels wereproduced under the conditions of example 1 modified in that the resinwas replaced with an epoxy resin consisting of 100 parts by weight ofepoxy resin (reference LY 556 sold by Ciba-Geigy), 90 parts by weight ofphthalic anhydride (reference: ARALDITE HY 917 sold by Ciba-Geigy) and0.5 parts by weight of tertiary amine (reference: ARALDITE DY 070 soldby Ciba-Geigy).

[0085] The measurements of the mechanical properties of the panelsobtained are given in table 2.

EXAMPLE 3

[0086] Filaments obtained under the conditions of example 1 were coatedwith the following first composition A and then with the followingsecond composition B (in percentages by weight): Composition A polyestertetraacrylate of molecular mass = 1000⁽¹⁾ 16 aromatic polyurethanehexaacrylate of 14 molecular mass = 1000⁽²⁾gamma-methacryloxypropyltrimethoxysilane⁽³⁾ 11gamma-glycidoxypropyltrimethoxysilane⁽⁴⁾ 10 4-octylphenyl ethyl ether⁽⁵⁾5 Composition B 4-octylphenyl ethyl either⁽⁵⁾ 5 mixture ofC,C,C-trimethylhexane-1,6-diamine, 14 of xylylenediamine and ofpara-tert-butylphenol⁽⁶⁾ trimethylolpropane trioctanoate⁽⁷⁾ 10ethoxylated (4EO) lauric alcohol⁽⁸⁾ 5 alkoxylated aromatic derivative⁽⁹⁾10

[0087] The compositions A and B had a viscosity of 78.4×10⁻³ Pa.s (78.4cP) and 216×10⁻³ Pa.s (216 cP) at 25° C., respectively, the ratio rbeing 1.02.

[0088] The filaments were assembled as strands which were wound asrovings.

[0089] The amount of fuzz, the stiffness, the loss on ignition, thelinear density and the tenacity were measured on the strands extractedfrom the rovings. The results of these measurements are given in table1.

[0090] Parallel-strand composite panels were produced from the strandsobtained, under the conditions of example 2.

[0091] The measurements of the mechanical properties of the panelsobtained are given in table 2.

EXAMPLE 4

[0092] Filaments under the conditions of example 1 were coated with thefollowing first composition A and then with the following secondcomposition B (in percentages by weight): Composition A polyestertetraacrylate of molecular mass = 1000⁽¹⁾ 20 aromatic polyurethanehexaacrylate of 10 molecular mass = 1000⁽²⁾gamma-methacryloxypropyltrimethoxysilane⁽³⁾ 11gamma-glycidoxypropyltrimethoxysilane⁽⁴⁾ 10 4-octylphenyl ethyl ether⁽⁵⁾5 Composition B mixture of C, C, C-trimethylhexane-1,6-diamine, 10 ofxylylenediamine and of para-tert-butylphenol⁽⁶⁾ trimethylolpropanetrioctanoate⁽⁷⁾ 12 ethoxylated (4EO) lauric alcohol⁽⁸⁾ 10 alkoxylatedaromatic derivative⁽⁹⁾ 8 C₁₆ alkylimidazoline¹⁰⁾ 4

[0093] The compositions A and B had a viscosity of 77.6×10⁻³ Pa.s (77.6cP) and 161×10⁻³ Pa.s (161 cP) at 25° C., respectively, the ratio rbeing 1.36.

[0094] The filaments were assembled as strands which were wound asrovings.

[0095] The amount of fuzz, the stiffness, the loss on ignition, thelinear density and the tenacity were measured on the strands extractedfrom the rovings. The results of these measurements are given in table1.

[0096] Composite panels were produced from the strands thus obtained,under the conditions described in example 1.

[0097] The measurements of the mechanical properties of the panelsobtained are given in table 2.

EXAMPLE 5

[0098] Composite panels were produced from the strands obtained inexample 4, under the conditions described in example 2.

[0099] The measurements of the mechanical properties of the panelsobtained are given in table 2.

EXAMPLE 6

[0100] Filaments obtained under the conditions of example 1 were coatedwith the following first composition A and then with the followingsecond composition B (in percentages by weight): Composition A polyestertetraacrylate of molecular mass = 1000⁽¹⁾ 22 aromatic polyurethanehexaacrylate of 8 molecular mass = 1000⁽²⁾gamma-methacryloxypropyltrimethoxysilane⁽³⁾ 11gamma-glycidoxypropyltrimethoxysilane⁽⁴⁾ 10 4-octylphenyl ethyl ether⁽⁵⁾5 Composition B mixture of C,C,C-trimethylhexane-1,6-diamine, 10 ofxylylenediamine and of para-tert-butylphenol⁽⁶⁾ trimethylolpropanetrioctanoate⁽⁷⁾ 12 ethoxylated (4EO) lauric alcohol⁽⁸⁾ 10 alkoxylatedaromatic derivative⁽⁹⁾ 12

[0101] The compositions A and B had a viscosity of 72.8×10⁻³ Pa.s (72.8cP) and 169.3×10⁻³ Pa.s (169.3 cP) at 25° C., respectively, the ratio rbeing 1.33.

[0102] The filaments were assembled as strands which were wound asrovings.

[0103] The amount of fuzz, the stiffness, the loss on ignition, thelinear density and the tenacity were measured on the strands extractedfrom the rovings. The results of these measurements are given in table1.

[0104] Composite panels were produced from the strands thus obtained,under the conditions described in example 1.

[0105] The measurements of the mechanical properties of the panelsobtained are given in table 2.

EXAMPLE 7

[0106] Composite panels were produced from the strands obtained inexample 6, under the conditions described in example 2.

[0107] The measurements of the mechanical properties of the panelsobtained are given in table 2.

EXAMPLE 8

[0108] Filaments obtained under the conditions of example 1 were coatedwith the following first composition A and then with the followingsecond composition B (in percentages by weight): Composition A polyestertetraacrylate of molecular mass = 1000⁽¹⁾ 18 aromatic polyurethanehexaacrylate of 18 molecular mass = 1000⁽²⁾gamma-methacryloxypropyltrimethoxysilane⁽³⁾ 11gamma-glycidoxypropyltrimethoxysilane⁽⁴⁾ 10 4-octylphenyl ethyl ether⁽⁵⁾5 Composition B C,C,C-trimethylhexane-1,6-diamine 44,9-dioxa-1,12-dodecanediamine 6 trimethylolpropane trioctanoate⁽⁷⁾ 15ethoxylated (4EO) lauric alcohol⁽⁸⁾ 13

[0109] The compositions A and B had a viscosity of 127×10⁻³ Pa.s (127cP) and 27×10⁻³ Pa.s (27 cP) at 25° C., respectively, the ratio r being1.10.

[0110] The filaments were assembled as strands which were wound asrovings.

[0111] The amount of fuzz, the stiffness, the loss on ignition, thelinear density and the tenacity were measured on the strands extractedfrom the rovings. The results of these measurements are given in table1.

[0112] Composite panels were produced from the strands thus obtained,under the conditions described in example 2.

[0113] The measurements of the mechanical properties of the panelsobtained are given in table 3.

EXAMPLE 9

[0114] Filaments obtained under the conditions of example 1 were coatedwith the following first composition A and then with the followingsecond composition B (in percentages by weight): Composition A polyestertetraacrylate of molecular mass = 1000⁽¹⁾ 18 aromatic polyurethanehexaacrylate of 18 molecular mass = 1000⁽²⁾gamma-methacryloxypropyltrimethoxysilane⁽³⁾ 11gamma-glycidoxypropyltrimethoxysilane⁽⁴⁾ 10 4-octylphenyl ethyl ether⁽⁵⁾5 Composition B C,C,C-trimethylhexane-1,6-diamine 10 trimethylolpropanetrioctanoate⁽⁷⁾ 15 ethoxylated (4EO) lauric alcohol⁽⁸⁾ 13

[0115] The compositions A and B had a viscosity of 127×10⁻³ Pa.s (127cP) and 23.8×10⁻³ Pa.s (23.8 cP) at 25° C., respectively, the ratio rbeing 0.88.

[0116] The filaments were assembled as strands which were wound asrovings.

[0117] The amount of fuzz, the stiffness, the loss on ignition, thelinear density and the tenacity were measured on the strands extractedfrom the rovings. The results of these measurements are given in table1.

[0118] Composite panels were produced from the strands thus obtained,under the conditions described in example 1.

[0119] The measurements of the mechanical properties of the panelsobtained are given in table 3.

EXAMPLE 10

[0120] Composite panels were produced from the strands thus obtained inexample 9, under the conditions described in example 2.

[0121] The measurements of the mechanical properties of the panelsobtained are given in table 3.

EXAMPLE 11

[0122] Filaments obtained under the conditions of example 1 were coatedwith the following first composition A and then with the followingsecond composition B (in percentages by weight): Composition A polyestertetraacrylate of molecular mass = 1000⁽¹⁾ 18 aromatic polyurethanehexaacrylate of 18 molecular mass = 1000⁽²⁾gamma-methacryloxypropyltrimethoxysilane⁽³⁾ 11gamma-glycidoxypropyltrimethoxysilane⁽⁴⁾ 10 4-octylphenyl ethyl ether⁽⁵⁾5 Composition B 4,9-dioxa-1,12-dodecanediamine 10 trimethylolpropanetrioctanoate⁽⁷⁾ 15 ethoxylated (4EO) lauric alcohol⁽⁸⁾ 13

[0123] The compositions A and B had a viscosity of 127×10⁻³ Pa.s (127cP) and 25.3×10⁻³ Pa.s (25.3 cP) at 25° C., respectively, the ratio rbeing 0.76.

[0124] The filaments were assembled as strands which were wound asrovings.

[0125] The amount of fuzz, the stiffness, the loss on ignition, thelinear density and the tenacity were measured on the strands extractedfrom the rovings. The results of these measurements are given in table1.

[0126] Composite panels were produced from the strands thus obtained,under the conditions described in example 2.

[0127] The measurements of the mechanical properties of the panelsobtained are given in table 3.

EXAMPLE 12

[0128] Filaments obtained under the conditions of example 1 were coatedwith the following first composition A and then with the followingsecond composition B (in percentages by weight): Composition A polyestertetraacrylate of molecular mass = 1000⁽¹⁾ 18 aromatic polyurethanehexaacrylate of 18 molecular mass = 1000⁽²⁾gamma-methacryloxypropyltrimethoxysilane⁽³⁾ 11gamma-glycidoxypropyltrimethoxysilane⁽⁴⁾ 10 4-octylphenyl ethyl ether⁽⁵⁾5 Composition B C,C,C-trimethylhexane-1,6-diamine 34,9-dioxa-1,12-dodecanediamine 4 trimethylolpropane trioctanoate⁽⁷⁾ 17ethoxylated (4EO) lauric alcohol⁽⁸⁾ 14

[0129] The compositions A and B had a viscosity of 127×10⁻³ Pa.s (127cP) and 30×10⁻³ Pa.s (30 cP) at 25° C., respectively, the ratio r being1.15.

[0130] The filaments were assembled as strands which were wound asrovings.

[0131] The amount of fuzz, the stiffness, the loss on ignition, thelinear density and the tenacity were measured on the strands extractedfrom the rovings. The results of these measurements are given in table1.

[0132] Composite panels were produced from the strands thus obtained,under the conditions described in example 1.

[0133] The measurements of the mechanical properties of the panelsobtained are given in table 3.

EXAMPLE 13

[0134] Composite panels were produced from the strands obtained inexample 12, under the conditions of example 2.

[0135] The measurements of the mechanical properties of the panels aregiven in table 3.

EXAMPLE 14

[0136] Filaments of obtained under the conditions of example 1 werecoated with the following first composition A and then with thefollowing second composition B (in percentages by weight): Composition Apolyester tetraacrylate of molecular mass = 1000⁽¹⁾ 14 aromaticpolyurethane hexaacrylate of 14 molecular mass = 1000⁽²⁾ bisphenol Fdiglycidyl ether⁽¹¹⁾ 8 gamma-methacryloxypropyltrimethoxysilane⁽³⁾ 11gamma-glycidoxypropyltrimethoxysilane⁽⁴⁾ 10 4-octylphenyl ethyl ether⁽⁵⁾5 Composition B mixture of C,C,C-trimethylhexane-1,6-diamine, 10 ofxylylenediamine and of para-tert-butylphenol⁽⁶⁾ isopropyl palmitate 15ethoxylated (4EO) lauric alcohol⁽⁸⁾ 13

[0137] The compositions A and B had a viscosity of 110×10⁻³ Pa.s (110cP) and 48.8×10⁻³ Pa.s (48.8 cP) at 25° C., respectively, the ratio rbeing 1.36.

[0138] The filaments were assembled as strands which were wound asrovings.

[0139] The amount of fuzz, the stiffness, the loss on ignition, thelinear density and the tenacity were measured on the strands extractedfrom the rovings. The results of these measurements are given in table1.

[0140] Composite panels were produced from the strands thus obtained,under the conditions described in example 1.

[0141] The measurements of the mechanical properties of the panelsobtained are given in table 3.

EXAMPLE 15

[0142] Composite panels were produced from the strands obtained inexample 14, under the conditions described in example 2.

[0143] The measurements of the mechanical properties of the panelsobtained are given in table 3.

EXAMPLE 16

[0144] Filaments obtained under the conditions of example 1 were coatedwith the following first composition A and then with the followingsecond composition B (in percentages by weight): Composition A polyestertetraacrylate of molecular mass = 1000⁽¹⁾ 20 aromatic polyurethanehexaacrylate of 10 molecular mass = 1000⁽²⁾gamma-methacryloxypropyltrimethoxysilane⁽³⁾ 11gamma-glycidoxypropyltrimethoxysilane⁽⁴⁾ 10 4-octylphenyl ethyl ether⁽⁵⁾5 Composition B mixture of C,C,C-trimethylhexane-1,6-diamine, 10 ofxylylenediamine and of para-tert-butylphenol⁽⁶⁾ isopropyl palmitate 12ethoxylated (4EO) lauric alcohol⁽⁸⁾ 10 alkoxylated aromaticderivative⁽⁹⁾ 8 C₁₆ alkylimidazoline⁽¹⁰⁾ 4

[0145] The compositions A and B had a viscosity of 73.4×10⁻³ Pa.s (73.4cP) and 75.2×10⁻³ Pa.s (75.2 cP) at 22° C., respectively, the ratio rbeing 1.36.

[0146] The filaments were assembled as strands which were wound asrovings.

[0147] The amount of fuzz, the stiffness, the loss on ignition, thelinear density and the tenacity were measured on the strands extractedfrom the rovings. The results of these measurements are given in table1.

[0148] Composite panels were produced from the strands thus obtained,under the conditions described in example 1.

[0149] The measurements of the mechanical properties of the panelsobtained are given in table 4.

EXAMPLE 17

[0150] Composite panels were produced from the strands obtained inexample 16, under the conditions described in example 2.

[0151] The measurements of the mechanical properties of the panelsobtained are given in table 4.

EXAMPLE 18

[0152] Filaments obtained under the conditions of example 1 were coatedwith the following first composition A and then with the followingsecond composition B (in percentages by weight): Composition A polyestertetraacrylate of molecular mass = 1000⁽¹⁾ 18 aromatic polyurethanehexaacrylate of 11 molecular mass = 1000⁽²⁾ bisphenol F diglycidylether⁽¹¹⁾ 8 gamma-methacryloxypropyltrimethoxysilane⁽³⁾ 10gamma-glycidoxypropyltrimethoxysilane⁽⁴⁾ 10 polyethylene glycol 300isostearate⁽¹²⁾ 5 Composition B mixture ofC,C,C-trimethylhexane-1,6-diamine, 10 of xylylenediamine and ofpara-tert-butylphenol⁽⁶⁾ isopropyl palmitate 10 ethoxylated (4EO) lauricalcohol⁽⁸⁾ 10 alkoxylated aromatic derivative⁽⁹⁾ 8

[0153] The compositions A and B had a viscosity of 93.4×10⁻³ Pa.s (93.4cP) and 73.2×10⁻³ Pa.s (73.2 cP) at 22° C., respectively, the ratio rbeing 1.35.

[0154] The filaments were assembled as strands which were wound asrovings.

[0155] The amount of fuzz, the stiffness, the loss on ignition, thelinear density and the tenacity were measured on the strands extractedfrom the rovings. The results of these measurements are given in table1.

[0156] Composite panels were produced from the strands thus obtained,under the conditions described in example 1.

[0157] The measurements of the mechanical properties of the panelsobtained are given in table 4.

EXAMPLE 19

[0158] Composite panels were produced from the strands obtained inexample 18, under the conditions of example 2.

[0159] The measurements of the mechanical properties of the panelsobtained are given in table 4.

EXAMPLE 20

[0160] Filaments obtained under the conditions of example 1 were coatedwith the following first composition A and with the following secondcomposition B (in percentages by weight): Composition A aliphaticpolyurethane hexaacrylate of molecular 10 mass = 800⁽¹⁴⁾ polyethertetraacrylate of molecular mass greater 22 than 1000⁽¹⁵⁾ bisphenol Fdiglycidyl ether⁽¹¹⁾ 8 gamma-methacryloxypropyltrimethoxysilane⁽³⁾ 10gamma-glycidoxypropyltrimethoxysilane⁽⁴⁾ 8 polyethylene glycol 300isostearate⁽¹²⁾ 4 Composition B mixture ofC,C,C-trimethylhexane-1,6-diamine, 9 of xylylenediamine and ofpara-tert-butylphenol⁽⁶⁾ isopropyl palmitate 12 ethoxylated (4EO) lauricalcohol⁽⁸⁾ 10 alkoxylated aromatic derivative⁽⁹⁾ 7

[0161] The compositions A and B had a viscosity of 162×10⁻³ Pa.s (162cP) and 66×10⁻³ Pa.s (66 cP) at 22° C., respectively, the ratio r being1.67.

[0162] The filaments were assembled as strands which were wound asrovings.

[0163] The amount of fuzz, the stiffness, the loss on ignition, thelinear density and the tenacity were measured on the strands extractedfrom the rovings. The results of these measurements are given in table1.

[0164] Composite panels were produced from the strands thus obtained,under the conditions described in example 1.

[0165] The measurements of the mechanical properties of the panelsobtained are given in table 4.

EXAMPLE 21

[0166] Composite panels were produced from the strands obtained inexample 20, under the conditions of example 2.

[0167] The measurements of the mechanical properties of the panelsobtained are given in table 4.

EXAMPLE 22

[0168] Filaments obtained under the conditions of example 1 were coatedwith the following first composition A and with the following secondcomposition B (in percentages by weight): Composition A aliphaticpolyurethane hexaacrylate of molecular 12 mass = 800⁽¹⁴⁾ polyethertetraacrylate of molecular mass greater 20 than 1000⁽¹⁵⁾gamma-methacryloxypropyltrimethoxysilane⁽³⁾ 10gamma-glycidoxypropyltrimethoxysilane⁽⁴⁾ 10 polyethylene glycol 300isostearate⁽¹²⁾ 5 polyethylene glycol 300⁽¹⁵⁾ 5 Composition Btrimethl-1,6-hexanediamine 7 isopropyl palmitate 12 ethoxylated (4EO)lauric alcohol⁽⁸⁾ 10 alkoxylated aromatic derivative⁽⁹⁾ 9

[0169] The compositions A and B had a viscosity of 110.4×10⁻³ Pa.s(110.4 cP) and 39×10⁻³ Pa.s (39 cP) at 220° C., respectively, the ratior being 1.19.

[0170] The filaments were assembled as strands which were wound asrovings.

[0171] The amount of fuzz, the stiffness, the loss on ignition, thelinear density and the tenacity were measured on the strands extractedfrom the rovings. The results of these measurements are given in table1.

[0172] Composite panels were produced from the strands thus obtained,under the conditions described in example 1.

[0173] The measurements of the mechanical properties of the panelsobtained are given in table 4.

EXAMPLE 23

[0174] Composite panels were produced from the strands obtained inexample 22, under the conditions of example 2.

[0175] The measurements of the mechanical properties of the panelsobtained are given in table 4.

[0176] In the above examples, it should be pointed out that the strandsobtained according to the invention can be easily handled. They have ahigh tenacity for a relatively low loss on ignition. Moreover, thestrands according to the invention exhibit good abrasion resistancemeasured by the small amount of fuzz recovered after passing over theturn rolls. It should be noted that the strand obtained according toexamples 4, 6 and 20 possesses good weavability and impregnability (lowintegrity after undergoing the abrasion test) and that the strand ofexamples 8, 9 and 11 exhibits good integrity before and after undergoingthe abrasion test.

[0177] Moreover, the strands according to the invention allow effectivereinforcement of organic materials, especially those based on apolyester or epoxy resin. The composites incorporating said strands havea high flexural modulus, in particular for polyester resins (of around40 000 MPa), this high modulus being maintained after aging. The shearstrength is also high, up to 90 MPa, in the composites based onpolyester resin, such a value being difficult to attain with glassstrands coated with an aqueous size. This strength value remains goodafter aging (less than 30% drop). (1) Sold under the reference “EBECRYL810” by Union Chimique Belge (2) Sold under the reference “EBECRYL 220”by Union Chimique Belge (3) Sold under the reference “SILQUEST Si A 174”by Witco OSI (4) Sold under the reference “SILQUEST Si A 187” by WitcoOSI (5) Sold under the reference “IGEPAL CO630” by Rhodia (6) Sold underthe reference “ANCAMINE 2089 M” by Air Products (7) Sold under thereference “TMP ESTER” by Lamberti (8) Sold under the reference “SIMULSOLP4” by Seppic (9) Sold under the reference “SIMULSOL BPPE” by Seppic(10) Sold under the reference “NEOXIL AO 83634” by DSM (11) Sold underthe reference “ARADITE GY 285” by Ciba-Geigy (12) Sold under thereference “2018 LDM” by Seppic (13) Sold under the reference “EBECRYL5129” by Union Chimique Belge (14) Sold under the reference “IRR 443” byUnion Chimique Belge (15) Sold under the reference “POLYGLYCOL PEG 300”by Clariant

[0178] TABLE 1 Ex. 1 Ex. 3 Ex. 4 Ex. 6 Ex. 8 Ex. 9 Ex. 11 Ex. 12 Ex. 14Ex. 16 Ex. 18 Ex. 20 Ex. 22 Fuzz (mg)  1  6  5  7  0.7  0.7  2.3  8  0 3.7  2  0.7  1.3 Stiffness 165 147 142 133 193 182 172 180 165 162 160142 152 (mm) (62) (62) (60) (60) (75) (83) (72) (65) (63) (60) (65) (60)(60) Loss on  0.55  0.53  0.53  0.51  0.61  0.55  0.54  0.52  0.48  0.53 0.47  0.51  0.49 ignition (%) Linear 302 312 301 306 309 302 300 306297 284 295 301 298 density (tex) Tenacity —  47.8  48.7 —  45.6  50.7 44.7  45.8  43.8  38.2  38.7  39.0  24.3 (g/tex) σ — (4.1) (1.5) —(2.0) (2.0) (2.2) (1.5) (2.0) (4.8) (5.7) (3.4) (6.6)

[0179] TABLE 2 Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 Ex. 7 Glass content  68.02   66.11   62.86   65.17   63.90   69.01   63.19 (% by weight)Resin polyester epoxy epoxy polyester epoxy polyester epoxy BENDINGStrength for 100% glass (MPa) before aging  3111.1  2709.1  2718.2 3143.7  2752.9  3011.9  2747.7 σ (90.4) (131.3) (124.9) (76.7) (121.6)(130.9) (184.8) after aging  2389.6  2380.0  2239.3  2137.7  2407.2 2303.9  2513.3 σ (48.0) (91.7) (83.9) (71) (41.7) (74.6) (202.1)Modulus (MPa) before aging 40439 38531 35820 38175 35978 39806 36184 σ(561) (285) (845) (1433) (524) (818) (1901) after aging 40316 3892936093 37273 36795 40790 35928 σ (1006) (349) (910) (847) (613) (1076)(2661) SHEAR Strength (MPa) before aging   89.4   81.7   80.0   86.7  82.6   90.2   79.9 σ (0.6) (0.7) (1.2) (0.9) (0.9) (0.9) (1.0) afteraging   64.9   48.5   48.6   67.2   70.3   68.9   65.5 σ (0.7) (0.8)(0.7) (0.8)   0.5 (1.1) (2.6)

[0180] TABLE 3 Ex. 8 Ex. 9 Ex. 10 Ex. 11 Ex. 12 Ex. 13 Ex. 14 Ex. 15Glass content   63.68   67.04   61.02   63.45   66.13   63.69   66.99  64.75 (% by weight) Resin epoxy polyester epoxy epoxy polyester epoxypolyester epoxy BENDING Strength for 100% glass (MPa) before aging 2682.4  3187.5  2755.8  2789.9  3155.3  2751.7  3137.1  2662.2 σ(103.6) (129.4) (73.4) (75.2) (91.3) (89.6) (146.8) (197.6) after aging 1916.2  2254.1  2357.7  1693.0  2373.0  2335.4  2260.0  2562.0 σ(135.6) (46.2) (44.2) (53.7) (72.5) (100.2) (64.3) (75.4) Modulus (MPa)before aging 35604 38716 33378 35112 37748 35207 40221.0 35961 σ (1777)(599) (502) (487) (979) (345) (866) (828) after aging 34499 37718 3291733967 36928 34717 38919.0 36178 σ (3080) (487) (782) (733) (729) (459)(699) (363) SHEAR Strength (MPa) before aging   79.5   84.8   79.4  77.8   84.1   81.4   89.3   80.2 σ (0.6) (1.3) (0.2) (0.2) (1.4) (0.6)(0.5) (1.9) after aging   36.1   64.1   58.9   29.8   59.9   55.6   67.0  72.7 σ (1.2) (1.10) (0.6) (1.0) (0.80) (0.7) (1.0) (0.8)

[0181] TABLE 4 Ex. 16 Ex. 17 Ex. 18 Ex. 19 Ex. 20 Ex. 21 Ex. 22 Ex. 23Glass content   65.00   62.56   66.3   64.24   67.8   64.77 (% byweight) Resin polyester epoxy polyester epoxy polyester epoxy polyesterepoxy BENDING Strength for 100% glass (MPa) before aging  3150.1  2817.0 3221.9  2798.8  3074.3  2827.1  3218.4  2824.8 σ (113.2) (140.0) (161)(133.5) (178.4) (112.2) (129.6) (70.8) after aging  2054.0  2146.0 2045.9  2646.0  2286.5  2603.0  2129.0  2557.7 σ (102.3) (43.8) (43.4)(97.7) (77.8) (52.6) (104.9) (111.1) Modulus (MPa) before aging 3747935584 39381 37285 36545 36978 40457 37778 σ (506) (889) (1015) (971)(2644) (476) (735) (477) after aging 35295  355.64 37529 37068 3481136711 38262 37622 σ (311) (540) (759) (851) (1117) (481) (913) (443)SHEAR Strength (MPa) before aging   85.0   88.5   84.8   83.3   86.9  83.4   86.7   83.2 σ (2.1) (1.4) (1.3) (0.7) (1.0) (1.4) (1.10) (0.40)after aging   67.6   69.2   64.6   70.9   67.7   71.1   65.0   70.0 σ(0.9) (0.60) (1.7) (1.10) (0.70) (0.4) (1.3) (0.80)

1. A glass strand coated with a sizing composition consisting of asolution whose solvent content is less than 5% by weight, this solutioncomprising at least 45% by weight of components capable of curing, thesecurable components being, in respect of at least 40% of them, componentswith a molecular mass of between 750 and 5000 and these curablecomponents comprising at least one mixture capable of curing: one ormore components having at least one acrylic and/or methacrylic reactivefunctional group and one or more components having at least one primaryamine and/or secondary amine reactive functional group.
 2. The glassstrand as claimed in claim 1, characterized in that at least 40% of thecurable components have at least two reactive functional groups chosenfrom acrylic, methacrylic, primary amine and secondary amine functionalgroups.
 3. The glass strand as claimed in either of claims 1 and 2,characterized in that more than 50% of the curable components having atleast one reactive functional group chosen from acrylic, methacrylic,primary amine and secondary amine functional groups.
 4. The glass strandas claimed in one of claims 1 to 3, characterized in that the mixturecomprises at least one component having at least two acrylic andmethacrylic reactive functional groups and having a molecular mass ofbetween 750 and
 5000. 5. The glass strand as claimed in one of claims 1to 4, characterized in that the content of component(s) having at leastone acrylic functional group and/or at least one methacrylic reactivefunctional group is between 15 and 60% by weight of the sizingcomposition.
 6. The glass strand as claimed in any one of claims 1 to 5,characterized in that at least 50% by weight of the curable componentshave at least two reactive functional groups chosen from acrylic andmethacrylic functional groups.
 7. The glass strand as claimed in one ofclaims 1 to 6, characterized in that the proportion of component(s)having at least one primary and/or secondary amine reactive functionalgroup is between 4 and 40% by weight of the sizing composition.
 8. Theglass strand as claimed in one of claims 1 to 7, characterized in thatthe ratio r of the number of (meth)acrylic reactive sites to the numberof primary and/or secondary amine reactive sites is between 0.15 and 3.9. The glass strand as claimed in one of claims 1 to 8, characterized inthat at least 20% by weight of the curable components have at least tworeactive functional groups chosen from acrylic and methacrylicfunctional groups and have a molecular mass of between 750 and
 5000. 10.The glass strand as claimed in one of claims 1 to 9, characterized inthat the sizing composition includes up to 8% by weight of at least onecatalyst.
 11. The glass strand as claimed in one of claims 1 to 10,characterized in that the composition includes at least one couplingagent in a proportion of between 0 and 30% by weight.
 12. The glassstrand as claimed in one of claims 1 to 11, characterized in that thecomposition includes at least one textile processing aid in a proportionof between 0 and 35%.
 13. The glass strand as claimed in one of claims 1to 12, characterized in that the composition includes up to 8% by weightof at least one film-forming agent.
 14. A sizing composition for glassstrand, consisting of a solution whose solvent content is less than 5%by weight, this solution comprising at least 45% by weight of componentscapable of curing, these curable components being, in respect of atleast 40% of them, components with a molecular mass of between 750 and5000 and these curable components comprising at least one mixturecapable of curing: one or more components having at least one acrylicand/or methacrylic reactive functional group and one or more componentshaving at least one primary amine and/or secondary amine reactivefunctional group.
 15. The composition as claimed in claim 14,characterized in that at least 40% of the curable components have atleast two reactive functional groups chosen from acrylic, methacrylic,primary amine and secondary amine functional groups.
 16. A process forproducing sized glass strands in which a multiplicity of streams ofmolten glass, flowing out from a multiplicity of orifices located at thebase of one or more bushings, is drawn in the form of one or more sheetsof continuous filaments, then the filaments are assembled into one ormore strands which are collected on a moving support, said processconsisting in depositing, on the surface of the filaments while they arebeing drawn and before the filaments have been assembled into strands,at least some of the sizing composition as claimed in either of claims14 and 15, the strand(s) being coated with the sizing composition at thelatest during collection of the strand(s).
 17. The process as claimed inclaim 16, characterized in that the composition is deposited in one stepon the surface of the filaments while they are being drawn and beforethe filaments are assembled into strands.
 18. The process as claimed inclaim 16, characterized in that a first stable composition having aviscosity of between 20 and 500 cP is deposited on the surface of thefilaments and at least one second stable composition, fed separatelyfrom the first, having a viscosity of between 20 and 500 cP is depositedon the surface of the filaments or of the strand(s) at the earliestwhile the first composition is being deposited and at the latest whilethe strand or strands is/are being collected, the difference inviscosity between the compositions deposited being less then 250 cP, themixture of the compositions deposited forming the sizing composition asclaimed in either of claims 14 and 15 and being curable at roomtemperature.
 19. The process as claimed in claim 18, characterized inthat the first composition comprises at least one component having atleast one acrylic and/or methacrylic reactive functional group and inthat the second composition comprises at least one component having atleast one primary amine and/or secondary amine reactive functionalgroup.
 20. A composite comprising at least one organic and/or inorganicmaterial and sized glass strands, characterized in that all or some ofthe glass strands consist of sized glass strands as claimed in one ofclaims 1 to 13.